Preparation of unsaturated alcohols and ethers

ABSTRACT

Unsaturated alcohols and ethers are prepared through the reaction of C4 to C6 aliphatic conjugated diolefins with water, a lower alkanol or mixtures thereof in the presence of a zero valent palladium based catalyst system. The preferred catalyst is tetrakis(tribenzylphosphine) palladium, tetrakis(diphenylalkylphosphine)palladium or tetrakis(triphenylphosphine)palladium alone or in combination with a basic material such as a quaternary ammonium hydroxide. Where one of the coreactants is water, the reaction is conducted in the presence of a solvent. The unsaturated alcohol and ether products can be catalytically hydrogenated to plasticizer alcohols and ether solvent media.

United States Patent [1 1 Romanelli June 3, 1975 PREPARATION OFUNSATURATED I ALCOHOLS AND ETHERS [75] Inventor: Michael G. Romanelli,New York.

[73] Assignee: Exxon Research and Engineering Company, Linden. NJ.

[22] Filed: June 18, 1973 [21] Appl. No.: 370.722

3.769.352. which is a continuation-in-part of Ser. No. 808.673. March19. 1969. Pat. No. 3.670.032.

[52] U.S. Cl 260/632 R [51] Int. Cl. C076 29/00 [58] Field ofSearch..... 260/614 R. 614 A. 614 AA.

260/632 R. 641 R. 642 R1252/431 P. 431 N 9/1970 Shryne 260/614 AA 4/1971Lloyd 260/614 AA OTHER PUBLICATIONS Takahashi et al.. I. TetrahedronLetters. No. 26, pp. 2451-2453. 1967. Takahashi et 211., 11. Bull. Chem.Soc., Japan. 41. 454-460. (1968).

Primary Examinerl-loward T. Mars Attorney. Agent. or F inn-Frank A.Aantoro [57] ABSTRACT Unsaturated alcohols and ethers are preparedthrough the reaction of C 4 to C s aliphatic conjugated diolefins withwater. a lower alkanol or mixtures thereof in the presence of a zerovalent palladium based catalyst system. The preferred catalyst istetrakis(tribenz vlphosphinel palladium.tetrakis(diphenylalkylphosphine)- palladium ortetrakis(triphenylphosphinelpalladium alone or in combination with abasic material such as a quaternary ammonium hydroxide. Where one of thecoreactants is water. the reaction is conducted in the presence of asolvent. The unsaturated alcohol and ether products can be catalyticallyhydrogenated to plasticizer alcohols and ether solvent media.

5 Claims. No Drawings i l PREPARATION UNSATURATED ALCOHOLS A AND ETHERSThis application is a division of US. Ser. No. 113,591, filed Feb. 8,1971 now US. Pat. No. 3,769,352 which, in turn, is acontinuation-in-part application of US. Ser. No. 808,673, filed Mar. 19,1969 now US. Pat. No. 3,670,032.

I BACKGROUND OF THE INVENTION 1. I Field of the Invention 'Thisinventionrelates to a process for the formation of unsaturated alcohols andethers. More particularly, this invention relates to the preparation ofunsaturated 'aliphatic'alcohols and ethers through the liquid phasereaction of aliphatic conjugated diolefins with water, aliphaticalcohols or mixtures thereof in the presence of a zero valvent palladiumbased catalyst system.

2. Description of the Prior Art Unsaturated aliphatic alcohols andethers are well known articles of commerce and have been preparedutilizing a variety of techniques. One previously proposedmethod for thepreparation of lower alkyl ethers involved the catalyzed dimerization ofbutadiene in the presence of a lower alkyl alcohol (see Takahasi,Tetrahedron Letters, p. 2451 (1967). The catalysts suggested for usewere tetrakis(triphenylphosphine palladium and bis (triphenylphosphine)palladium maleic anhydride adduct. While the catalyst systems served topromote the reaction to the desired ether products, the yields wererelatively small based upon the amount of palladium employed.

SUMMARY OF THE INVENTION Now, in accordance with the present invention,it has.

been found that both unsaturated alcohols and unsaturated ethers can bereadily formed through the catalyzed dimerization of conjugatedaliphatic diolefms in the presence of water, a lower alkyl alcohol, ormixtures thereof. The reaction is conducted in the liquid phase;normally, in the presence of a reaction diluent. Most preferably, thereaction system is homogeneous and the reaction is conducted at atemperature less than about 160C. in the substantial absence of oxygen.The preferred catalysts are tetrakis(tribenzylphosphine)palladium,tetrakis(diphenylakylphosphine)palladium ortetrakis(triphenylphosphine)palladium alone or in combination with abasic cocatalyst.

The manner in which the reactions proceed is demonstrated in thefollowing representative equations:

Equationl illustrates the reaction of two moles of butadiene with waterto form 1-octa-2,7-dienol. Equation 11 such as 1,3,7-octatriene are alsoformed. The starting olefin is preferably a C to C conjugated diolefinichydrocarbon. Examples of useful olefin materials include acyclicmaterials such as butadiene, isoprene and piperylene.

When an alcohol is empolyed as a coreactant, it is preferred that thealcohol be a lower acyclic or alicyclic monoalcohol having the generalformula ROH wherein R designates a monovalent straight chain, branchedchain or cyclic alkyl radical having from 1 to 8, preferably 1 to 5carbon atoms. The reaction rate varies markedly with the type of alcoholcoreactant used. For example. reactions wherein a straight chainalcohol, e.g., or methanol, is used proceed in a rapid feshion; however,when the alcohol is a branched chain material, such as tertiary butylalcohol, the reaction proceeds relatively slowly. The palladium basedcatalyst employed is decomposed to metallic palladium when contactedwith oxygen. Hence, maximum catalyst efficiency is secured when thediolefin, water and alcohol reagents are stripped prior to use to removeany dissolved oxygen. Oxygen removal can be achieved by sparging withnitrogen or other inert gas.

The instant reaction may be carried out in bulk; that is, in the absenceof a solvent or in the presence of an organic diluent that does notdecompose the zero valent palladium based catalyst. Reactions involvingan alkyl alcohol can be carried out in the absence of a diluent in thatolefinic material is readily soluble in the alcohol and the desiredhomogeneous system is secured. When water is empolyed as the processcoreactant or in situations wherein appreciable quantities of water arepresent within the reaction zone, a solvent system should be usedbecause the diolefin is substantially insoluble in water. Heterogeneousreaction systems should, in general, be avoided as the complex palladiumcatalyst is preferentially soluble in organic materials. Hence, areaction between a diolefin and water will not proceed at a commericallyviable rate in the absence of a co-solvent for both the water and theolefin since the palladium catalyst will tend to collect in the diolefinlayer.

With the exception of nitrogen-containing materials such as amines,amides, nitriles, etc., any type of material that will solubilize thediolefin and the hydroxy containing coreactant may be used as theprocess solvent. Alcohols and ethers, especially lower alkyl alcoholsand ethers having from 1 to 5 carbon atoms, are the preferred reaction"solvents. Most preferably, branched chain alcohols, e.g., secondary andtertiary alcohols, especially tertiary alcohols, are used because, whileparticipating in the reaction, they do so at a relatively slow rate.Useful solvents include isopropanol, t-butanol, tetrahydrofuran, etc.

The ratio of process reactants to solvent is not critical and may varyover a wide range. Ordinarily only a sufficient quantity of solvent isused to insure the desired single phase reaction system. Typically, in areaction system wherein water is used as a coreactant, the reactionsystem, before addition of diolefin, will be composed of from 15 to 50volume preferably 20 to 30 volume of water with the balance of thesystem i f made up of solvent. In water-containing systems, generallyabout 0.5 to 2.0 moles of butadiene are used per liter of solvent. Mostpreferably from 1.0 to 1.5 moles of diolefin are used per liter ofsolvent. In systems wherein water is not used as the coreactant, themolar ratio of diolefm to alcohol within the reaction zonecan varybetween about 0.01:1 to 3:1, preferably 0.1:1 to 1:1.

The process is conducted in the presence of a catalyst system composedof a zero valent palladium material. that is, zero valent palladium or amaterial that will generate zero valvent palladium at reactionconditions, a phosphine or isonitrile activator and, optionally, a basiscocatalyst material. Materials that will generate the desired zerovalent palladium at reaction conditions include materials such asbis(pi-ally)palladium, tetrakis(- tribenzylphosphine)palladium,tetrakis(diphenylalkylphosphine)palladium,tetrakis(phenyldialkylphosphine)palladium,tetrakis(trialkylphosphine)palladium andtetrakis(triphenylphosphine)palladium.

The activator compounds that can be employed in conjuction with thesource of zero valent palladium are phosphine and isonitrile materials,preferably compositions having the general formulas:

wherein R R R and R are monovalent, substituted or unsubstituted organicradicals having from 1 to 20, preferably 1 to 14, carbon atoms perradical Preferably, R R R and R are monovalent acyclic or alicyclicalkyl radicals having from 1 to 20, preferably 1 to 14 and mostpreferably l to 12 carbon atoms, such as methyl, propyl, isobutyl,cyclohexyl, etc.; phenyl radicals; monovalent alkylaryl radicals havingfrom 7 to 12, preferably 7 to 10, carbon atoms, e.g., tolyl, xylyl,ethylphenyl, etc., and monovalent aralkyl radicals having from 7 to 12,preferably 7 to 10, carbon atoms, such as benzyl, ethylbenzyl,diethylbenzyl, etc.

lsonitrile compounds are conveniently prepared by heating a primaryamine with chloroform and sodium hydroxide. The phosphine activatormaterials are generally prepared by reacting a phosphorous halide, e.g.,phosphorous trichloride, with an alkyl or aryl organometallic compounds,such as butyl lithium, phenylmagnesium chloride, etc. Representativeexamples of useful activator compounds include triphenylphosphine,tricyclohexylphosphine, tributylphosphine, diethyl phenylphosphine,methyldiphenylphosphine, tris(paratoly )phosphine, tris( metatolyl)phosphine, tris( 4- methylcyclohexyl)phosphine, tris(xylyl)phosphine,triethylphosphine, tribenzylphosphine, tris(phenylethyl)phosphine,methylisonitrile, ethylisonitrile, tbutylisonitrile,cyclohexylisonitrile, phenylisonitrile, p-tolylisonitrile, etc.

The preformance of the catalyst system can be greatly enhanced by usingeither an organic or inorganic base material in conjunction with thezero valent palladiumactivator system. Preferred basic materials includequaternary ammonium hydroxides having from 4 to 20, preferably 8 to 10,carbon atoms, quaternary ammonium alkoxides having from 4 to 20preferably 8 to 12, carbon atoms, alkali and alkaline earth metalhydroxides, and alkali and alkaline earth metal alkoxides having from 1to 10 carbon atoms. Since the use of inorganic hydroxides normallyadversely affects the solubility of the diolefm reagent within thereaction system, it is preferred that organic base materials, especiallyquaternary ammonium hydroxides, and alkoxides, be used as the processcocatalysts. Useful cocatalyst materials include tetraalkylammoniumhydroxides, tetraalkylammonium alkoxides, alkylpyridinium hydroxides,trialkylaralkylammonium hydroxides, trialkylaralkylammonium alkoxides,alkylpyridinium alkoxides, and alkali and alkaline earth metal oxides,hydroxides, and alkoxides such as sodium potassium and lithiummethoxide, ethoxide. isopropoxide, t-butoxide. etc.

The palladium catalyst is ordinarily employed in amounts ranging fromabout 0.0001 to 0.01 mole of catalyst per liter of alcohol and/orsolvent present within the reaction zone. In most instances. thepalladium catalyst is insoluble at concentrations greater than about0.01 mole of catalyst per liter of solvent and/or alcohol. It ispreferred that about 0.001 mole of catalyst be used per liter of solventand/or alcohol present within the reaction zone.

The concentration of the activator within the reaction zone can varyover a wide range. When a phosphine material is used, it is preferredthat it be employed in molar excess relative to the zero valentpalladium material. Up to about moles of phosphine compound may be usedper mole of zero valent palladium compound. Preferably, at least about 1to 10 moles phosphine activator are used per mole of zero valentpalladium material. When an isonitrile activator is used, it ispreferred that at least about 1 mole of isonitrile compound be employedper mole of zero valent palladium material. Preferably, about 1 to 4moles of isonitrile activator compound are used per mole of zero valentpalladium compound. When large excesses of isonitrile compound are usedrelative to the zero valent palladium material, the reaction tends tostart rapidly but then stops after a relatively brief reaction period.The source of zero valent palladium and the activator compound may becombined in a single complex of molecule, such astetrakis(tribenzylphosphine)palladium ortetrakis(triphenylphosphine)palladium. In such situations, it is notessential that additional amount of activator be employed; however, itis ordinarily preferred to use greater than stoichiometric amounts ofactivator compound.

The basic cocatalyst may be used at concentrations substantiallyidentical to or higher than the palladiurr catalyst concentration. Atleast about 0.0001 mole 01 base is used per liter of alcohol or solvent.The upper limit on base concentration may vary over a wide range as itis possible to use more than about 0.1 mole of base per liter of solventor alcohol. However, the presence of a basic material adversely affectsthe solubility of the olefin in thereaction system. Hence, it isordinarily desirable to maintain the base concentration at the lowes'effective level consistent with a desirable reaction rate for the amountof olefin dissolved within the reactior system.

The reaction is conducted in the liquid phase at tem peratures belowabout C. Although the reactior proceeds at a much faster rate atelevated tempera tures, the palladium catalyst tends to be inactivated atemperatures much above about 160C. Typically, tht reaction is carriedout at a temperature ranging be tween about 0 and 160C, preferablybetween 50 ant 140C. The reaction pressure, that is the pressure maintained within the reaction zone, may vary over a Wldl range as bothatmospheric and superatmospheric pres sures may be used. Typically, thepressure within thr reaction Zone is the autogenous pressure exerted byth' reactants and'so'lvent at the reaction temperature. Th length of thereaction period depends upon a numbe of process variables. In mostinstances, high produc 6 yields are secured at the above describedtemperature pentane layer w th w h d ith wat nd th and pressureconditions within about 0.1 to 60 hours. d i d v n i m s lfate. The emne was then More typically, substantial product yields are securedevaporated from the reaction product. within from 0.5 to 20 hours at theabove temperature The resulting product (3.0 grams) was subjected to andpressure conditions. 5

gas chromatographic, infrared and nuclear magnetic The unsaturatedalcohol and ether compounds PI resonance spectral analysis and was foundto contain duced according to the process of this invention have 659 f lll i 79 Wt. f 1- i y varied uses- Principally, the Composition y bedienol and 15.5 wt. of bis(2,7-octadienyl) ether. The hydrogenated inthe liquid Phase in the Presence of a unsaturated alcohol was formed ata rate of 0.233 typical hydrogenation catalyst such as nickel, platinum10 grams f alwho] per gram f catalyst per hour and a OI. palladium andreduced to the Corresponding Satuof grams of product per gram ofpalladium rated alcohols and ethers. The alcohol product can be wassecured reacted with phthalic anhydride to form useful polyvinylchlorideplasticizer materials. Additionally,the satu- EXAMPLE 2 rated alcoholscan be used as ingredients in cosmetic Following the general procedureof Example 21 formulationsThe saturated ethers may be employed ries ofexperiments were conducted wherein butadiene for solvent applications,particularly as constituents in was reacted with water in the presenceof an isopropapaint or varnish compositions. nol diluent. In each casetetrakis(triphenylphosphine)- palladium was used as the catalyst. Sodiumhydroxide g gg i igg cocatalyst was used in Run No. 2. The conditions atwhich each of the experiments were carried out as well The inventionwill be further understood by referas the results of the experiments areset forth in Table ence to the following examples. 1 below.

TABLE I \+H 0 (ph ph d (011.).011011 M MOE Morm mom A B C D wt t Yield01B percen 1120, (CHahCHOII, Temp.. 'Ilmo, Product, (L/g. GJg. g.- ml.ml. 0. hrs. g. A B C D catalyst Pd 17.1 40 120 60 21.0 10.0 10.4 15.460.9 21.8 236 0.0 100 120 00 42.0 10.0 10.0 13.0 59.4 9.2 21.0 235 14.0100 120 60 50.0 5.1 4.8 17.1 62.7 0.3 9.7 100 7.7 8 24 23.5 1.81 14.522.2 28.8 4.2 10.5 114 5.2 20 24 -80 56.0 3.13 18.2 17.9 37.3 8.4 18.7203 I Initial charge-not. all consumed. 5 2.0 ml. 50% NaOH added.Temperature not maintained during entire period.

40 've ess of the EXAMPLE 1 The above data clearly Indicate the effectin palladium catalyst and base in promoting the formation A nitrogenpurged mixture consisting of 1-Ol47 of both unsaturated ethers andalcohols. As shown in grams of te51kmtriphehylphosphihe)Pflhadium, 174Table l, the major portion of the products secured from grams ofbutadiene, 5O milliliters of tetmhydrofurah the reaction is made up ofthe desired unsaturated alcoand 10 milliliters of water were introducedinto the reh l d ethers action vessel of a typical Parr pressureapparatus. After EXAMPLE 3 addition of the catalyst, process reagentsand solvent, the reaction vessel was shaken and simultaneously heated to60C. The reaction was continued at 60C. for 16.5 hours. Upon completionof the reaction period, the reaction vessel was vented and the liquidcontents diluted with three volumes of water. Thereafter, the organiclayer was separated from the water layer and the latter extracted withpentane. The resulting Following the procedure of Example 1 a number oftests were conducted wherein butadiene was reacted with water in thepresence of a tertiary butanol diluent. The catalyst employed wastetrakis(triphenylphosphine)palladium. Benzyltrimethyl ammoniumhydroxide was used as cocatalyst in Run No. 2. The results of the testsand conditions at which the experiments were carried out are set forthin Table 11 below.

. TABLE 11 Ph P Pd Lil... (CHDICOH Mon mgcwm M M A. B C D wt t Yield ofB percen (1 1 ,1 Pd, 1120. (01191011011, Temp., Time, Product, G./gG./g. Run No g. 1111. ml. 0. hrs. 1;. A B C D catalyst Pd 0.0335 4.4 2040 25 60.0 0.3 3.8 35.5 18.0 7.4 3.1 32.8 0.0300 8.8 20 40 25 69.0 1.391.0 .19.! 10.9 18.0 6.9 74.9 0.0875 18.7 25 125 22.5 8.5 14.0 42.8 18.316.9 183 0.0728 11.1 b0 60 8.3 0.3 10.0 57.2 19.4 1.4 2.36 25.6 0. 063112. 0 50 100 60 18. 0 2. 4 l1. 4 42. 6 10. 5 13. 4 16. 1 0.0832 11.8 1 0100 80 00.0 4.4 12.4 38.9 12.9 19.0 20.6 223 0.0214 4.0 N 30 80 17.5 3.211.5 40.4 12.8 19.6 60.5 657 lchar 0-1101 n11 consunmd. df x xi l. of buzyl trhuuthyl ammonium hydroxide flddfid.

The above data clearly indicate the utility of the reaction for theformation of unsaturated alcohols and ethers. As is evidenced from thedata, the use of a tertiary alcohol, namely tertiary-butanol, as thereactioon of the tests wherein the base material was present, higheryields of product were secured as compared with substantially identicaltests wherein no base was used. As shown in Runs 9-12, the presence ofthe basic solvent clearly resulted in the formation of much lesscocatalyst served to promote the formation of the prodether product.Using the tertiary-butanol solvent sysuct within relatively briefreaction times even when tern, the selectivity of the process wasgreatly directed branched chain alkanols were used. to the formation ofthe unsaturated alcohol. Runs 1 and 2 demonstrate the desirable effectssecured with the EXAMPLE 5 use ofa quaternary ammonium base cocatalyst.1n Run a nitrogen purged mixture of tetrakis(tribenzylphos- 2 where1n abenzyltnmethylammonium hydroxide phine)pal1adium, butadiene and 100 ml.of methanol cocatalyst was used, the rate of formation of alcohol wereplaced into a pressure bottle, stirred magnetically per gram ofpalladium per hour was appoximately twice and heated in an oil bath.Upon completion of the reacthat secured with an identical run wherein noquatertion period, the reaction vessel was vented and the liqnaryammonium hydroxide was used. uid contents diluted was 3 volumes ofwater. Thereafter the organic layer was separated from the water layerEXAMPLE 4 and the latter extracted with pentane. The combined Followingthe general procedure of Example 1 a organic and pentane layers werethen washed with number of tests were conducted wherein butadiene waswater and dried over magnesium sulfate. The pentane reacted with thevarious types of aliphatic monoalwas then evaporated from the reactionproduct. The cohols at C. In each of the tests, the catalyst emproductwas subjected to gas chromatography and the ployed wastetrakis(triphenylphosphine)palladium results summarized in Table IV.

TABLE IV Product Exp. [(C H cHfl PhPd Butadiene T tl-methoxy-2,7-octadiene 3-methoxy 1,7-octadiene g/g g. g. C. hrs g. wt.g/g Pd/hr. wt Pd/hr.

alone or in combination with benzyltrimethylam- The above tests clearlypoint out both the substantial monium methoxide. The results of the testand condiactivity of tetrakisltflbeflFylphosPhine)Pwadiurn a tions atwhich the experiments were carried out are set catalyst and deslrblhtyusmg as hlgh aleacnon temperature as 1s conslstent w1th catalyststab1l1ty, e.g. forth 1n Table 111 below. 0

TABLE 111 Grams Prod/Gram Pd/Hr. Grams Alcohol Milliliters Grams TimeGrams l-Octadienyl 3-Octadienyl Run Catalyst Type Alcohol ButadieneHours Product Ether Ether 1 0.0974 Methanol 100 8.7 1.87 8.20 460 22.6 20.0975 Methanol 100' 8.5 1.87 9.00 466 58.0 3 0.0484 Ethanol 100 10.33.00 3.40 212 8.58 4 0.0479 Ethanol 100 9.2 3.00 4.80 293 27.7 5 0.0419n-Propanol 100 10.0 3.00 0.00 6 0.0480 n-Propanol 100" 10.5 3.00 8.10447 23.2 7 0.0483 n-Butanol 100 10.6 3.00 2.10 124 5.51 8 0.0487n-Butanol 100" 10.0 3.00 6.00 372 16.0 9 0.0465 lsopropanol 100 10.1 3.00 0.00 10 0.0448 lsopropanol 100" 10.5 3.00 1.00 447 23.2 1 1 0.0481t-Butanol 80 7.3 17.3 0.00 12 0.0497 t-Butanol 80" 8.0 19.0 2.79

"3 milliliters of a 40 wt. 7r solution 01' bcnzyltrimethylammoniummethuxidc also added. "1 milliliter of 0.186 N henzyltrimcthylammoniummethoxide in methanol also added.

65 The above tests clearly po1nt out the des1rab1l1ty of EXAMPLE 6 usinga basic cocatalyst in conjunction with the general zero valentpalladium/activator catalyst system. In each Following the generalprocedure of Example 5, a series of reactions were run in which thecatalyst was tetrakis(diphenylalkylphosphine)palladium; L Pd where Ldiphenylalkylphosphine. The results are listed in Table V.

olefin and water, said solution being free of dissolved oxygen, togetherwith a solvent for said conjugated diolefin and water, said solvent tobe selected from the TABLE V Product S-methoxy-lfl- LtPd catalyst1-methory-2J-octad1ene octndlene Butadlene, Temp., Time, Wt. (L/g. Wt.(L/g.

Exp L equals Grams g. 0. hrs Grams percent Pd/hr. percent Id/lrr 1C1HrhPCll3 0. 1827 12. 3 140 0. 26 11. M 81. 6 1, 760 12. 6 270CdIlhPCrHs 0. 147B 12. 0 140 0. 14. 48 82. 0 3,500 11. 1 470 8(CdiuhP-rlCdiu 0. 0870 X0. 6 140 0. 10. 31. 81 1 4,280 8. 3 430 aHmP 5CaHQzP-nCnHu 0. 0810 10. 1 140 0. 25 9.00 88. 9 5, 580 8. 0 560 6...Calla zP-nCnllu 0. 0703 10. 8 140 0. 10. 88. 2 7,230 8. 1 600 7(hllshP-mCzfllu 0.0059 10. 3 140 0. 33 10.50 83. 8 5,420 9. 3 570 8.(CdIshP-SC d1 0. 117B 13. 5 120 0. 1b 13. 02. 6 7, 360 6. 8 540 Theabove tests clearly show the substantial activity 20 oftetrakis(diphenylalkylphosphine)palladium compounds as catalysts, andthe increase in catalytic activity as the straight chain alkyl groupincreases in length from 1 to 16 carbon atoms. A substantial increase incatalytic activity is also obtained when the alkyl group is eithercyclic, experiment 4, or branched, experiment 8.

EXAMPLE 7 Following the general procedure of Example 5, a series ofreactions were run in which the catalyst wastetrakis(phenyldialkylphosphine)palladium, L Pd whereL=phenyldialkylphosphine. The results are listed in group consisting ofisopropanol, t-butanol and tetrahydrofuran, in the presence of acatalyst system comprised of a zero valent palladium material, selectedfrom the group consisting of tetrakis (triphenylphosphine) palladium,tetrakis (tribenzylphosphine) palladium, tetrakis(diphenylalkylphosphine) palladium, tetrakis (phenyldialkylphosphine)palladium, tetrakis (trialkylphosphine) palladium, and a basiccocatalyst selected from the group consisting of tetralkyl andtrialkylaralky] ammonium hydroxides and alkoxides having from 4 to 20carbon atoms at a temperature ranging from 0 to 160C.

2. The process of claim 1, wherein the zero valent palladium material istetrakis (triphenylphosphine) pal- Table VI. 35 ladium.

TABLE VI Exp. L Pd Catalyst Butadiene T t Product Catalystl-methoxy-2,7-octadiene 3-methoxy-l,7-octadiene L= g. g. C. hrs. wt. g/gPd/hr. wt. g/g Pd/hr.

l C l-l P(C 1-1 0.0863 9.5 140 0.50 10.41 72.7 1190 13.4 220 2 C HP(n-C..H1.-i)2 2.6 140 0.33 8.00 87.9 1640 7.9 150 The above testsclearly show the activity of tetra(phenyldialkylphosphine)palladiumcompounds as catalysts.

EXAMPLE 8 Following the general procedure of Example 6, a series ofreactions were run in which the catalyst wastetrakis(trialkylphosphine)palladium, L Pd where L=trialkyl phosphine.The results are listed in Table VI].

3. The process of claim 1, wherein said conjugated diolefin isbutadiene.

4. The process of claim 2 wherein said conjugated diolefin is butadiene.

5. A process for the formation of unsaturated alcohols which comprisescontacting in the liquid phase a solution of butadiene and water, saidsolution being free of dissolved oxygen, together with isopropanol orTABLE Vll Exp. L Pd Catalyst Butadiene T t Product Catalyst1-methoxy-2,7-octadiene 3-methoxyl ,7-octadiene L= g. g. C. hrs. g. wt.g/g Pd/hr. wt. g/g Pd/hr.

l 'P(n-C,H,,) 0.1493 12.8 140 0.25 12.96 75.9 2260 14.0 420 2 P(n-C|1),-, 0.1168 10.5 140 0.65 5.35 88.9 940 9.6

The above tests clearly show the activity oftetrakis(trialkylphosphine)palladium compounds as catalysts.

What is claimed is:

1. A process for the formation of unsaturated alcohols which comprisescontacting in the liquid phase a solution of a C to C acyclic aliphaticconjugated dit-butanol, in the presence of tetrakis (triphenylphosphine)palladium and a basic cocatalyst selected from the group consisting ofbenzyltrimethyl ammonium'hydroxide, and benzyltrimethyl ammoniummethoxide at a temperature range from 50 to C.

1. A PROCESS FOR THE FORMATION OF UNSATURATED ALCLHOLS WHICH COMPRISESCONTACTING IN THE LIQUID PHASE A SOLUTION OF A C4 TO C6 ACYCLICALIPHATIC CONJUGATED DIOLEFIN AND WATER, SAID SOLUTION BEING FREE OFDISSOLVED OXYGEN, TOGETHER WITH A SOLVENT FOR SAID CONJUGATED DIOLEFINAND WATER, SAID SOLVENT TO BE SELECTED FROM THE GROUP CONSISTING OFISOPROPANOL, T-BUTANOL AND TETRAHYDROFURAN, IN THE PRESENCE OF ACATAYLST SYSTEM COMPRISED OF A ZERO VALENT PALLADIUM MATERIAL, SELECTEDFROM THE GROUP CONSISTING OF TETRAKIS (TRIPHENYLPHOSPHINE) PALLADIUM,TETRAKIS (TRIBENZYLPHOSPHINE) PALLADIUM, TETRAKIS(DIPHENYLALKYLPHOSPHINE) PALLADIUM, TETRAKIS (PHENYLDIALKYLPHOSPHINE)PALLADIUM, TETRAKIS (TRIALKYLPHOSPHINE) PALLADIUM, AND A BASICCOCATALYST SELECTED FROM THE GROUP CONSISTING OF TETRALKYL ANDTRIALKYLARALKYL AMMONIUM HYDROXIDES AND ALKOXIDES HAVING FROM 4 TO 20CARBON ATOMS AT A TEMPERATURE RANGING FROM 0* TO 160*C.
 1. A process forthe formation of unsaturated alcohols which comprises contacting in theliquid phase a solution of a C4 to C6 acyclic aliphatic conjugateddiolefin and water, said solution being free of dissolved oxygen,together with a solvent for said conjugated diolefin and water, saidsolvent to be selected from the group consisting of isopropanol,t-butanol and tetrahydrofuran, in the presence of a catalyst systemcomprised of a zero valent palladium material, selected from the groupconsisting of tetrakis (triphenylphosphine) palladium, tetrakis(tribenzylphosphine) palladium, tetrakis (diphenylalkYlphosphine)palladium, tetrakis (phenyldialkylphosphine) palladium, tetrakis(trialkylphosphine) palladium, and a basic cocatalyst selected from thegroup consisting of tetralkyl and trialkylaralkyl ammonium hydroxidesand alkoxides having from 4 to 20 carbon atoms at a temperature rangingfrom 0* to 160*C.
 2. The process of claim 1, wherein the zero valentpalladium material is tetrakis (triphenylphosphine) palladium.
 3. Theprocess of claim 1, wherein said conjugated diolefin is butadiene. 4.The process of claim 2 wherein said conjugated diolefin is butadiene.